Lubricating composition



Patented May 4, 1943 UNITED STATES PATENT ILUBRICATING COMPOSlTIQN U 7 Carl F. Prutton, Cleveland lieights and Albert K. Smithj-Shaker Heights, Ohio, assignors, by

. .mesne assignments, to The LubrL-ZolDevelopment Corporation, Cleveland; Ohio, at corporation of Delaware- No Drawing. .Applicatlon'November12,1940,

' Serial No.365,224 1 r Y 1 Claims. {01.252 59 our co-pending application Serial No. 241,606,

filed November 21, 1938, now issued as Patent No. 2,255,085.

It has been explained that the reason why such compounds thus improve the extreme pressure characteristics of the lubricant probably is due to the fact that such addition agents chemically react with the bearing surfaces under the conditions imposed by relative movement and extreme pressure between the bearing surfaces to form a microscopic film of a metallic halide which prevents seizing between the bearing'surfaces by acting as an anti-fluxing agent.

The halogenated carbon ringcornpoun'ds were indicated as preferable in said patents due to the fact that such compounds fare relatively stable, i. e., they do not readily hydrolyze in the presence of moisture which usually occurs'in varying quantities in mineral oils. In other words, the halogenated carbon ring compounds are sufilciently stable so that decomposition andattack thereof upon'the metallic surfaces occurs only in the areas where extreme pressure is encountered. i. e.,"on the bearing surfaces.v

One theory of theaction of halogen compound's. specifically chlorinecompoun'dsfin increasing film strength, assumes that, as above indicated, under the stress of the rubbing action of bearing surfaces in motion under load, chlorides of the bearing metals are formed on their surfaces and exert an anti-fluxing effect in'preventing subsequent fusing of the two surfaces.-

( RC1 +HzO HCl+ROH (2) M+HCl- M+H where R is an organic radicle and M the metals of the bearing surfaces.

is one of (Note.-'-'-The' hydrogen evolved by me n ably would act 'toredu'ce one ormore oitheor;

ganic compounds rather than to' appear a's'ffree hydrogen.) L V V w i I .The correctnessof the foregoing theory issubstantia'tedby theiactthat when achlorinated hydrocarbon is added to ahydrocarbon mineral [oil andthemixture thoroughly freed from mois tureby the a'ction'of dehydrating agents, the

.film strength is no more than that of theoil alone. Exposure of the mixture'tothe atmosF phere so that it may absorb a'slight amount of moisture will thencause an'increase in the film Since the presence'of a large amount of moisture and especially of free; water is objectionable ina lubricant besides beinga highly variable factorin normal service, itisadv-isable to sup- ..ply an "oilsoluble substitute forthe-same. 1

It is the principal object of this; invention,

therefore, to provide a lubricating composition 7 as the" type utilizing halogenatedorganic compounds as the extreme ipressure addition agentbut so modified as to-be eilec'tive in'the manner defined without being-'dependent'upon the presence in the lubricating composition of some additiori material such as water;

Other object'sofj our invention will appear 'as I the description proceeds.

.To the'accomplishment of the foregoing and related ends, said invention, then," "consists of the meanshereinafter fully described and par:

tioularly pointed outin the claims. I

.The following description sets forth in'd'etail one approved combination .of. ingredients embodyingvour inventionigisuch disclosedmeans constituting, however, but one of various forms in which the principle of the invention may be ing organic compounds and more specifically,

oxygen and halogen bearing-organic ring compounds,'either used valoneorincorporated with any suitable oil-base.

The "oxygen which is included in the molecule of, the addition agent acts-to increase the effectiveness of the latter in raising the film strength of'a mineral oil to which the addition agent is added or to improve the lubricating propertiesv 2 of the halogenated compound when used without the addition of some other lubricant. The

oxygen probably acts in the same way as water at the exact point where required:' and y'- Included in Class II are two principal types 01' compounds, vizz- Compounds in which all of i I The foregoing compounds may also be classifled according to the nature of the attachment of the oxygen to the compound, viz:

I'. Directly attached to one or more carbon Second: The molecule is more strongly ab sorbed by metal surfaces than similar halogen compounds which do not contain oxygen.

The latter circumstance enhances the effect of small amounts of such compounds because it is equivalent to an increase in concentration of the compound at the bearing surfaces.

We have found that certain oxygen-containing organic ring compounds which have been chlorinated and added to a lubricating oil are capable of improving the properties of such oil, particularly when employed for thin-film" lubricating purposes.

have been chlorinated and added to the lubricating oil have been found to improve the properties thereofto an even greater extent than certain similar chlorinatedhydro-carbons, notably when added in very small amounts., g

The halogen and oxygen containing' organic ring compounds added to a suitable oil base-are,

as above indicated, preferably offthe chlorinated species and particularly the compounds which have been found to produce very satisfactory re-f suits, may be classified as follows; viz:

I. "C arbon ring" type compounds (a) 01' the aromatic, or allied type, including oxygen and halogen bearing derivatives of benzene, diphenyl, naphthalene; anthracene, etc., and homologs of them, also such derivatives of coml pounds of the bridged ringtype, such 1 as the terpenes, and related com (b) Of the. class including such derivatives The addition'of these certain, oxygen containing organic ring compounds which ofthe cycle-aliphatic compounds such as cycloparamns, cyclo-oleflnes, cycloacetylenes. Examples of thisclass arev oxygen and halogen-bearing derivatives of hydrogenated aromatic compounds, such as the following:

(1) Hydrogenation products of benzene (e. g. cyclohexane, cyclohexene, cyclohexadiene) I f;(2) Hydrogenation products of I "naphthalenefet g. decahydronaphthalene, tetrahydronaphthalene etc.) 7

(3) Naphthenes, naphthenic acid,

etch A I v (c) 0! mixed type such as oxygen and halogen-bearing derivatives of indene,

atoms, as in the case of (1') Ethers and analogous compounds (2') Compounds containing the EC-OH radicle, such as alcohols and other derivatives of carbinol phenols, cresols, naphthols etc.)

(3') Compounds containing the carbonyl (=C=O) radicle, such as aldehydes. ketones, organic acids, esters and salts of organic acids, thio-acids and esters of thio-acids (4') Compounds in which oxygen forms a a part of the ring structure, e. g. furan and its derivatives, anthraquinone, etc.

II. Indirectly attached through the means of some other atom, i. e., in the form of an inorganic radicle, e. g.:

Amide Arsenate Ars'enite Chlorate Chlorite Cyanate Hydroxylamine Hypochlorite Nitrate Nitrite Nitro a Nitroso Perchlorate Phosphate Phosphite Sulphate Sulphite' a Sulphinicacid sulpho'n'e Sulphonic acid sulphoxide Thiocyanate Isothiocyanate Thio-sulphate Thio-phosphate Isocyanate.

7 3. An .ester formed by the combination of an aromatic alcohol (either mono-hydric or poly-hydric) with an organic acid ofeither I the fatty or aromatic type.

In addition to the substituents-containing' oxygen, other substituents may also be present without destroying, and in certain cases, improving the eflfect on the lubricating qualities of the oil such as other aryl groups, alkyl groups, and amino (including Glass and substituted'amino groups,-imino, azo, hydrazo, hydrazine, nltrile, mercapto, polysulphide.

sulphide,

Specific examples of compounds of'the various Stearic acid 7 Stearic acid derivatives Phenyl stearic acid. Phenyl mercapto stearic acid Xenyl stearic acid Naphthyl stearic acid Tolyl stearic acid -Furoic acid Cinnamic acid Phthalic acid Toluic acid Mercapto rosolic acid Among the esters and salts, halogen derivatives 01' which are likewise suitable for use as addition agents, are the esters and salts which may be derived from the aromatic acids listed immediately above and mono and polyhydric alcohols, or other hydroxy compounds (including phenols). Specific examples of such alcohols and hydroxy compounds are those specifically identified under (6) in next column.

Among the salts of aromatic acids, the halogenbearing derivatives of which may also'be 'employed as addition agents, are the salts of the aromatic acids listed above, including the sodium, calcium aluminum, magnesium, zinc and lead salts, and salts derived from ammonia, substi tuted ammonias, and other organic bases such as quinoline and pyridine. w

A very important group of esters, halogenbearing derivatives of which are particularly suited for use as addition agents, especially in certain types of lubricants, are the esters of alcohols or the benzenoid type. Specific examples of such alcohols are the following: 7 I

Benzyl alcohol Phenyl ethyl alcohol Benzhydrol Tri phenyl carbinol Phenyl propyl alcohol Phenyl benzyl alcohol Fu'ri'uryl alcohol Naphthobenzyl alcohol Cinnamyl alcohol accordance with our invention. The following is a classification of these unsaturated oxygen compounds along with speciflc examples of the various groups within this sub-class:

(1) Unsaturated alcohols, e. g.

Vinyl ethyl alcohol Allyl. alcohol Crotonyl alcohol Oleyl alcohol Propargyl alcohol (2) Unsaturated aldehydes, e.- g.

Acrolein Crotonaldehyde Hexadienal Octatrienal v Citral Propargylic aldehyde 1 (3) Unsaturated ketones, e. g. v Allyl acetone Di-allyl ketone Mesityl oxide Phorone Vinyl lauryl ketone Acetylenic ketones (e. g. R-LECCOR') such as Allylene methyl ketone Allylene lauryl ketone (30) Ketenes Ketene Acetyl ketene (4) Unsaturated ethers, e. g.

Di-vinyl ether Di-allyl ether Allyl ethyl ether Vinyl ethyl ether Allyl iso-amyl ether Allyl lauryl ether Propargyl ethyl ether (5) Unsaturated acids, e. g.

Vinyl acetic acid Vinyl acrylic acid, Vinyl glycolic acid Acrylic acid Crotonic acid 'Oleic acid Linolenic acid Maleic acid Fumaric acid Linoleic acid Elaeostearic acid Propiolic acid Stearolic acid (6) Unsaturated esters, e. g.

' (a) 1 Esters of'unsaturated acids (e. 3. those listed under (5) above as well as unsaturated aromatic acids such as cinnamic and coumaric) with monoand poIy-hydric alcohols, or other hydroxy compounds (including phenols). Examples 01' such alcohols and hydroxy compounds are: r

Methyl alcohol Ethyl alcohol Propyl alcohols Butyl alcohols Amyl acohols Lauryi alcohols Cetyl alcohols Benzyl alcohol Furi'uryl alcohol 3 Tetrahydrofuri'uryl alcohol Ethylene glycol Propylene glycol Di-ethylene glycol Glycerol 'Erythritol Phenol- Polyhydroxy-benzenes Alkylated phenols Naphthols Unsaturated alcohols (e. g. those listed under 1) above) (b) Esters of unsaturated alcohols (e. 2. those listed under 1) above) with organic acids, either aliphatic or aromatic, or with inorganic acids. Examples are:

or such acids Aliphatic acids, including:

Saturated acids, such as:

Acetic acid Propionic acids Butyric acids Laurie acids Palmitic acid stearic acid Oxalic acid Citric acid Lactic acid Glycolic acid Malonic acid Unsaturated acids, such as those listed under above Aromatic acids, including:

Benzoic acid Phthalic acids Salicyclic acid Anthranllic acid Cinnamic acid Cyclo-aliphatic acids, including;

Naphthenic acids Hexahydrobenzoic acid Heterocyclic 'acids including:

Furoic acid Pyrrol carboxyllic acids Inorganic acids, including:

Hydro-halogen acids Oxy-halogen acids Sulphurous acid Sulphuric acid 'Ihiosulphuric acid; Carbonic acid Thiocarbonic acids Hydrogen sulphide Phosphorous acid Thiophosphorous acids Phosphoric acid Thiophosphoric acids Cyanic acid Thiocyanic acid Hydrocyanic acid Boric acid (7) Salts of unsaturated acids, including the Ammonium and substituted ammonium Sodium Calcium Aluminum Magnesium Zinc Lead V Salts of unsaturated acids generally, and more specifically of such acids as those listed under (5) above and of unsaturated aromatic acidsl In addition to the compounds listed above, commercial products comprising complex mixtures of unsaturated oxygen-bearing organic compounds may be used as the "unsaturated" reactant Examples of such materials are-the fatty oils of unsaturated character, e. g.

Castor oil Chinawood oil Corn 011 Cottonseed oil Croton oil Lard oil Linseed oil Menhaden fish oil Rape seed oil Soya bean oil Sperm oil Useful additional unsaturated oxygen com--' I pounds which may be'derived from any of the above fatty oils are, e. g.

(l) Acids, extracted from the oils by direct in" drolysis, or by saponiflcation and subsequent hydrolysis, or otherwise. (2). Esters, produced by ester-ifying'the acids of (l) e. g. to form esters analogous to any of those listed under (6) 'in Tabie No. 2. (3) Soaps, produced by saponifyins the oils directly or by neutralizing the acids of (l) with alkalies, e. g. to form salts analogous to those listed under ('7) in Table No. 2.

The unsaturated oxygen compounds arevoi particular importance and may, therefore, be classified in further detail according to the nature of the attachment of the oxygen atom to the mole- I cule, viz:

' Table No. 3

v I, Directly attached to one or more carbon atoms, as in the case of: J

(1') Ethers and analogous compounds (2') Compounds containing the -C-OH f radicle, such as alcohols and other derivatives ofcarbinol (including phenols, oresols, naphthols etc.)

(3') Compounds containing 'the carbonyl C=O radicle, 'suchas amides, aldehydes, ketones, organic acids, esters ,and salts of organic acids (including such salts of both inorganic and organic bases), thic acids and esters and salts of thio acids (4') Compounds in which oxygen forms .a part of the ring structure, e. g.v

furanand its derivatives, etc. I

(5') Compounds with an inorganic radi-,

c1e where the oxygen is directly attached to a carbon atom, e. g. ,-Arse 'nltes I Hypochlorites Phosphites Thiophosphates Thiophosphites B-hydroxylamines. I Borates r II'.-Indirectly attached through the meansof some other atom, i, e., in the iorm oi an inorganic radicle, e. g.: j

Arsenate I V Chlorate v i Chlorite' Cyanate a-hydroxylamine Nitrate Nitrite Nitro Nitroso Oxime Perchlorate Phosphate Sulphate Sulphite Sulphinic acid Sulphone Sulphonic acid Sulphoxide Thiophosphate Thiophosphite Thio sulphate (Norm-This class includes bases with inorganic oxy-acids) salts of organic v In addition to the unsaturated compounds above described, certain unsaturated cyclic com- 7 Pounds are also of use, such as the cyclo-olefines (e. g. cyclo-hexene) and derivatives of them.

As a matter of convenience, the halogen and oxygen-containing substituted diphenyls, as well as the halogen and oxygen-containing substituted benzenes where two or more phenyl groups are directly linked, may be inclusively referred to as phenyls.

This invention also contemplates the use of halogen-bearing acids (and salts and esters derived from them) which may be derived from compounds formed by condensing unsaturated acids (such as those included among the ,unsaturated oxygen-bearing. compounds referred to above) with an aromatic compound in the preshalogen and oxygen-containing substituted polyence of a catalyst such as anhydrous aluminum matic acid, ester, or salt, with an unsaturated aliphatic compound) will be found in the copending application of Carl F; Prutton, Ser. No. 216,153, filed June' 27, 1938.

As previously indicated, the foregoing so-called addition agents may, for most uses, be added in minor amounts to other lubricants such as mineral oil, fish oil, lard oil, castor oil, rape-seed oil, etc., and in some cases, depending upon the character of use, as well as the character of the selected agents, the'latter may be efiectively used in their pure state. i v

The optimum amount of the halogen compound to be employed is usually dependent upon various considerations such as its cost,'the character of the selected compounds, the character of the addition agent to which the same is added and more particularly, the character of the use to which the same isput. For mostuses. since the cost of such halogen compounds is usually considerably greater than lubricantssuch as mineral oil, optimum results are obtained by using minimum quantities to these halogenated addition agents. For the purpose of lubricating and reducing the friction between relatively moving parts of an internal combustion engine such as crank case bearings, piston and cylinder surfaces, as well as piston rings and valves, a composition according to our invention comprises a major proportion of a suitable oil base such as mineral oil and concentrations of from one-fourth of 1% to 2% of halogen compounds of the above'defined type. It the valve structure of the engine is to be lubricated separately from the remainder of the mechanism by means acting in an auxiliary fashion such as by the addition of the lubricating composition to the engine fuel, the composition for such purposes will preferably contain a larger amount of such halogen compounds, 1. e. from about 2% to about 10%. a

When lubricating bearing surfaces such as gears and the like where extreme temperatures are usually not encountered a composition comprising a major proportion of a, suitable oil base and a total of less than about 20% of at least one halogen and oxygen-containing organic compound of the enumerated class will be found very satisfactory.

When combined with a lubricating oil such as mineral oil, the optimum amount of the halogen compound to be employed will depend largely upon the halogen content of the particular compound, its physical characteristics and especially its eiiect on the viscosity of the oil to which it is added. When addition agents of the above eral oil, the limit of the amount of such compounds which may be added and which will produce improved results depends in a large measure upon the reduction in viscosity of the composition caused by the addition of such compounds. When, however, the more viscous compounds are employed, or where the particular use does not require thick film lubrication, the so-called addition agents may, as previously indicated, be employed in their pure state.

Experiments have shown that when compounds which readily hydrolize, such as chlorinated open chain compounds, are added to the only base, hydrolysis will take place to such an extent that the metal parts of any machine being lubricated will be seriously attacked and corroded by the acid generated. On the. other hand, the addition of chlorinated organic ring compounds of the above enumerated class does not cause corrosion.

Certain of the halogen and oxygen-bearing open chain or aliphatic compounds, in their pure state, or when added to a suitable base do result, however, in a lubricant particularly suitable for certain purposes. Examples of the foregoing are halogenated fatty oils such as chlorinated cotton-seed oil and chlorinated cocoanut oil. As above indicated, such compounds readily hydrolize and While thus not preferred as a lubricant for use in the crank case of internal combustion engines, are nevertheless, admirably suited for use as lubricants in metal working such as drawing, extruding, rolling, etc., where the lubricant isin contact with the metallic surface for only relatively a short length of time and where the very slight amount of corrosion which may result is not particularlyobjectionable. Furthermore, such compounds are admirably suited for use in lubricants in die drawing or similarly working certain corrosion resistantmaterials such as stainless steel and the like.

With regard to the stability oi the organic ring compounds contemplated, the most resistant to hydrolysis of the halogen are those in which the halogen is directly attached to an atom which is part of a benzenoid ring structure. Examples of such ring structuresare aryl groups such as the phenyl and naphthyl groups. In any case, for most uses, it is preferred to have the halogen attached to an. atom which is part of an organic ring structure and especially a sixmembered organic ring structure.

The compositions comprising our invention have certain advantages when used as a lubricant of which the following maybe mentioned: First: By the use of this composition, it is possible to extend the pressure range between the bearing surfaces because of the reduced tendency for bearing surfaces so lubricated to become scored or to seize at higher pressures than are allowable with-ordinary lubricants.

Second: The friction between the bearing surfaces is reduced, especially in the higher presbearing derivatives of which are contemplated for use as addition agents in the preparation of lubricating compositions in accordance with our invention. Many of these'materials themselves, 1. e., the unhalogenated materials named, as well as the halogen-free analogs of the halogenated or halogen-bearing materials named; may be employed to advantage in lubricating compositions since many of such possess valuable properties as addition agents.

These unhalogenated materials may be used as the sole addition agent to impart improved lubricating properties to a mineral oil (or other lubricating medium) or may advantageously be used in conjunction with other addition agents, such as organic halogen compounds, organic phosphorus compounds (e. g. esters of phosphoric and phosphorous acids), organic sulphur compounds, soaps, oiliness agents, oxidation inhibitors, viscosity index improvers, or such other addition agents as may be employed for the same or other purposes. a

Other modes of applying the principle of our invention may be employed instead of the one explained, change being made as regards the materials employed, provided the ingredients stated by any of the following claims or the equivalent of such stated ingredients be employed We, therefore, particularly point out and distinctly claim as our invention:

1. A lubricating composition comprising in combination, a major proportion of a suitable oil base and a minor proportion of a halogen and oxygen bearing aromatic compound containing the carbonyl radical.

2. A lubricating composition comprising in combination, a major proportion of a suitable oil base and a minor proportion or a halogen bearing aromatic aldehyde.

combination a major proportion of a suitable oil 3. A lubricating composition comprising a major proportion of a suitable 011 base and a minor proportion of an oxygen and halogen-bear ingorganic ring compound containing the carbonyl V 1 radical. I 4. A lubricating composition comprising in combination a major proportion of a suitable oil base and alminor proportion of a halogen bearing organic compound includinga o =o group directly attached to a ring structure.

5. A lubricating composition comprising in base and a minor proportion of a halogen hearing organic compound including a group directly attached to a benzenoid ring structure.

6. A lubricating composition comprising in combination a major proportion of a suitable oil a base anda minor proportion of ahalogen bearing organic compound including a CARL F. PRU'I'I'ON.- ALBERT K. SMITH. 

